Dissociation of diimide

Abstract

Parts of the potential energy surface of N2H2 have been studied using CASSCF- and contracted CI-methods. Of particular interest was the concerted dissociation of cis- and trans-diimide into N2 and H2, since the trans-dissociation is symmetry allowed and the cis-dissociation forbidden. Three different saddle points were located, of which only one, of C2υ- symmetry, is a true transition state. Elaborate numerical gradient methods using exact Hessians and update procedures had to be used to find these saddle points on the unexpectedly complex N2H2-surface. The barrier height with respect to trans-diimide is 61 kcal/mol after vibration correction. Since this energy is higher than the barrier for interconversion, cis- and trans-diimide have the same transition state. It is further found that diimide preferably dissociates stepwise, by losing one hydrogen at a time, rather than in a concerted way. This conclusion is drawn basically because the geometry of the transition state for the concerted dissociation has a very long H-H distance of 5.6 a.u. The N-H bond energy in trans-diimide is 56 kcal/mol after vibration correction.